CN106395900B - A kind of method of impurity in removal oxygen vanadium sulfate crystals - Google Patents
A kind of method of impurity in removal oxygen vanadium sulfate crystals Download PDFInfo
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- CN106395900B CN106395900B CN201610994016.8A CN201610994016A CN106395900B CN 106395900 B CN106395900 B CN 106395900B CN 201610994016 A CN201610994016 A CN 201610994016A CN 106395900 B CN106395900 B CN 106395900B
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- 239000013078 crystal Substances 0.000 title claims abstract description 116
- JYKIWJXDKPVNQZ-UHFFFAOYSA-L [O-]S([O-])(=O)=O.O.[V+5] Chemical compound [O-]S([O-])(=O)=O.O.[V+5] JYKIWJXDKPVNQZ-UHFFFAOYSA-L 0.000 title claims abstract description 98
- 239000012535 impurity Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 238000001914 filtration Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 239000012047 saturated solution Substances 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000005287 vanadyl group Chemical group 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052720 vanadium Inorganic materials 0.000 abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 13
- 230000008025 crystallization Effects 0.000 abstract description 13
- 238000005406 washing Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000011651 chromium Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 8
- 239000007788 liquid Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- KZNFRTXTQCISLO-UHFFFAOYSA-N oxovanadium;sulfuric acid Chemical compound [V]=O.OS(O)(=O)=O KZNFRTXTQCISLO-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- ZMFKXOMVFFKPEC-UHFFFAOYSA-D [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [V+5].[V+5].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZMFKXOMVFFKPEC-UHFFFAOYSA-D 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000011712 cell development Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 238000005213 imbibition Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000036186 satiety Effects 0.000 description 1
- 235000019627 satiety Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of minimizing technology of impurity in oxygen vanadium sulfate crystals, and the described method includes washing to remove the crystallization water of the first oxygen vanadium sulfate crystals and the impurity of plane of crystal, and the second oxygen vanadium sulfate crystals are obtained by filtration.The minimizing technology of impurity, can directly remove impurity element from oxygen vanadium sulfate crystals in the oxygen vanadium sulfate crystals of the present invention, improve the content of vanadium of oxygen vanadium sulfate crystals, simplification of flowsheet, reduces production cost, have good economy.
Description
Technical field
The present invention relates to field of hydrometallurgy, more particularly, is related to a kind of side for removing impurity in oxygen vanadium sulfate crystals
Method.
Background technology
For battery as a kind of emerging energy-storage system, it is all to have that service life is long, capacity is big, power is big, security is high etc.
More advantages, can be widely used in peak load regulation network, public transport airborne power supply, wind energy solar power energy-storage system etc..Mesh
The main reason for preceding restriction vanadium cell development is that its cost remains high, and basic reason is that the manufacturing cost of electrolyte is excessive, existing
Stage prepares the process of electrolyte, is to prepare high-purity vanadic anhydride raw material (to refer to Publication No. CN103482702A first
The Chinese patent method and vanadium cell high concentration electrolyte of high-purity vanadium oxide " prepare "), using high purity vanadic anhydride as
Basis prepares LITHIUM BATTERY vanadic sulfate, and prepare high purity vanadic anhydride process often relate to return molten, isolation of purified, precipitation,
Calcining etc. multiple steps, process is numerous and diverse, technological process is long and clean after effect it is undesirable, major impurity such as chromium, iron content is higher,
The presence of iron and chromium can seriously reduce the energy efficiency and corroding electrode material of vanadium cell, the serious fortune for influencing vanadium cell system
OK.
The removal of impurities of vanadic sulfate at present is broadly divided into two kinds, and one kind is (to include the conjunction of vanadic anhydride and vanadium in the feed
Lattice liquid) removal of impurities, have main steps that and vanadic anhydride is returned molten or precipitating reagent is directly added into qualifying liquid, such as magnesium salts, aluminium
The anionic impurities such as silicate, chromate, phosphate radical in the removing solution such as salt and calcium salt, then pass through acid precipitation and remove big portion
The cation impurity divided, such as sodium, potassium, calcium, magnesium (refer to a kind of Chinese patent " high concentration of Publication No. CN103515642A
The preparation method of high-purity vanadium battery electrolyte "；Study on Preparation Technology [J] steel vanadium titaniums of the high-purity ammonium metavanadates of Hou Haijun,
2013,34 (3)), this method technological process is long, operating process is complicated and impurity-eliminating effect is undesirable and introduce new impurity from
Son.Another impurity-removing method is mainly the method by extracting-back extraction, although this method eliminates leachate removal of impurities, ammonium salt
Precipitation, return the technical process such as molten, simplifies production technology, has saved the production time, and preparation process does not introduce other impurities, but extracts
Take and asked with ion exchange there are treating capacity is small, expensive reagents, cost are higher, the purity of degradation manipulation environment and product is not high
(Chinese patent with reference to Publication No. CN103151549A is " a kind of to prepare high-purity vanadium cell electricity based on extracting-back extraction system for topic
The method for solving liquid ")；In addition with directly going deimpurity method in oxygen vanadium sulphate solution.
Above impurity-removing method there are it is respective the shortcomings that, be limited its industrial applications, hinder vanadium to a certain extent
The development of battery.
The content of the invention
It is above-mentioned existing in the prior art it is an object of the present invention to solving for the deficiencies in the prior art
One or more problems.For example, impurity is directly removed from oxygen vanadium sulfate crystals it is an object of the present invention to providing one kind
The method of element.
To achieve these goals, the present invention provides a kind of minimizing technology of impurity in oxygen vanadium sulfate crystals.The side
Method includes washing to remove the crystallization water of the first oxygen vanadium sulfate crystals and the impurity of plane of crystal, and the second vanadic sulfate is obtained by filtration
Crystal.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, it is described to wash to remove first
The step of impurity of the crystallizations water of oxygen vanadium sulfate crystals and plane of crystal, can include：The first vanadic sulfate is washed with absolute ethyl alcohol
Crystal, so as to remove the crystallization water of the first oxygen vanadium sulfate crystals and the impurity of plane of crystal.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals, the absolute ethyl alcohol and first are removed according to the present invention
The liquid-solid ratio of oxygen vanadium sulfate crystals can be 0.5~1.0mL/g.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, it is described to be washed with absolute ethyl alcohol
The wash time of first oxygen vanadium sulfate crystals can be 3~5min.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, and the method can also include
Second oxygen vanadium sulfate crystals are washed with pure vanadic sulfate saturated solution.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, and the vanadic sulfate saturation is molten
The concentration of liquid can be 3~4mol/L.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, and pure vanadic sulfate saturation is molten
Liquid and the liquid-solid ratio of second oxygen vanadium sulfate crystals can be 1.0~1.5ml/g.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals, the pure vanadic sulfate are removed according to the present invention
The wash time that saturated solution washs second oxygen vanadium sulfate crystals can be 3~5min.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, and the method can also include
After the step of washing second oxygen vanadium sulfate crystals with pure vanadic sulfate saturated solution, filter and dry, obtain
Three oxygen vanadium sulfate crystals.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, and first vanadic sulfate is brilliant
Body is prepared by following steps：Oxygen vanadium sulphate solution containing impurity element is evaporated to supersaturated solution, adds crystal seed,
Decrease temperature crystalline obtains the first oxygen vanadium sulfate crystals.
One embodiment of the method for impurity in oxygen vanadium sulfate crystals is removed according to the present invention, it is described containing impurity element
K containing 0.005%~0.1% Cr, 0.005%~0.1% Na and 0.005%~0.1% in oxygen vanadium sulphate solution.
Remove one embodiment of the method for impurity in oxygen vanadium sulfate crystals according to the present invention, Seed charge for 8~
10g/L, 1~2 DEG C/h of cooling rate.
Compared with prior art, impurity method can be directly from oxygen vanadium sulfate crystals in present invention removal oxygen vanadium sulfate crystals
Middle removal impurity element, improves the content of vanadium of oxygen vanadium sulfate crystals, and simplification of flowsheet, reduces production cost, has well
Economy.
Embodiment
Hereinafter, it will be described in detail with reference to exemplary embodiment and remove impurity in oxygen vanadium sulfate crystals according to the present invention
Method.
Oxygen vanadium sulphate solution is grown up, increasingly during crystallization separates out oxygen vanadium sulfate crystals with the forming core of crystal
More impurity elements can become entrained in the vanadic sulfate crystallization water and plane of crystal, wherein being present in acid system with Cr, K, Na etc.
In impurity element based on.The present invention washs oxygen vanadium sulfate crystals by using ethanol, fills the crystallization water in oxygen vanadium sulfate crystals
The removing divided, gained crystal removes the alcohol of remnants, dries again with pure vanadic sulfate saturated solution washing and filtering after filtering
It can obtain the higher oxygen vanadium sulfate crystals of purity afterwards.
Absolute ethyl alcohol water imbibition is strong, and absolute ethyl alcohol can capture the partially crystallizable of oxygen vanadium sulfate crystals during washing
Water, while remove the magazine element included in the crystallization water.
An exemplary embodiment according to the present invention, the method for impurity includes in removal oxygen vanadium sulfate crystals of the invention
Step：
(1) wash to remove the crystallization water of the first oxygen vanadium sulfate crystals and the impurity of plane of crystal, the second sulphur is obtained by filtration
Sour vanadyl crystal.
In the present embodiment, the step of washing the impurity with the crystallization water of the first oxygen vanadium sulfate crystals of removing and plane of crystal
Including：The first oxygen vanadium sulfate crystals are washed with absolute ethyl alcohol, so as to remove the crystallization water and crystal table of the first oxygen vanadium sulfate crystals
The impurity in face, wherein, the agitator treating time is 3~5min, and the agitator treating time is more than 3min can reach removing impurity substantially
Effect, but overlong time can increase equipment loss and corresponding cost, and the agitator treating time, 3~5min can reach preferable effect
Fruit；The liquid-solid ratio of absolute ethyl alcohol and the first oxygen vanadium sulfate crystals is 0.5~1.0mL/g, is more than 0.5mL/g removal of impurities effects in liquid-solid ratio
Fruit is obvious, and liquid-solid ratio is excessive, that is, increases ethanol consumption, can not only increase cost, but also brings problem to subsequent handling,
Liquid-solid ratio, which is set to 0.5~1.0mL/g, can reach preferable effect.Absolute ethyl alcohol washs the solution after the first oxygen vanadium sulfate crystals
In contain impurity, can be by recycling ethanol after being dehydrated rectifying.
(2) configuration concentration is the pure vanadic sulfate saturated solution of 3~4mol/L, is stirred with pure vanadic sulfate saturated solution
Mix the second oxygen vanadium sulfate crystals of washing.Wherein, the agitator treating time is 3~5min, and the agitator treating time substantially may be used more than 3min
To reach the effect for removing impurity, but overlong time can increase equipment loss and corresponding cost, agitator treating time 3~5min energy
Enough reach preferable effect；The liquid-solid ratio of pure vanadic sulfate saturated solution and the second oxygen vanadium sulfate crystals is 1.0~1.5ml/
G, obvious more than 1.0mL/g impurity-eliminating effects in liquid-solid ratio, liquid-solid ratio is excessive, that is, increases pure vanadic sulfate saturated solution
Dosage, this can not only increase cost, but also bring problem to subsequent handling, and liquid-solid ratio is set to 1.0~1.5mL/g and can reach
Preferable effect.
(3) filter and dry, drying temperature is 50~60 DEG C, and the time is 30~60min, obtains the 3rd vanadic sulfate crystalline substance
Body.The drying temperature excessive time, which passes, can make vanadic sulfate generation hardened, change the water solubility of vanadic sulfate, drying temperature is too low
The time too short water that cannot remove plane of crystal well, and drying temperature is set to 50~60 DEG C, the time can for 30~60min
Reach preferable effect.
First oxygen vanadium sulfate crystals can be prepared by following steps：By the oxygen vanadium sulphate solution containing impurity element
Supersaturated solution is evaporated to, adds crystal seed, decrease temperature crystalline obtains the first oxygen vanadium sulfate crystals.；Wherein, the sulphur containing impurity element
K containing 0.005%~0.1% Cr, 0.005%~0.1% Na and 0.005%~0.1% in sour vanadyl solution；Crystal seed
Addition is 8~10g/L, 1~2 DEG C/h of cooling rate.Crystal seed requirement is qualified vanadic sulfate product.
In the present embodiment, compared to the first oxygen vanadium sulfate crystals, the reduced rate of Cr is 30 in the 3rd oxygen vanadium sulfate crystals
The reduced rate that the reduced rate of~50%, Na are 30~60%, K is 30~60%.
Above-mentioned example embodiment for a better understanding of the present invention, carries out further it with reference to specific example
Explanation.
Example 1
Oxygen vanadium sulphate solution containing impurity element (Cr 0.223%, K 1.22%, Na 1.35%) is evaporated to satiety
And state, relative to 1mol vanadium ions in supersaturated solution, 10L is taken, 100g crystal seeds is added, is dropped with 1 DEG C/h cooling rates
Temperature crystallization, obtains the first oxygen vanadium sulfate crystals.Wherein, the K containing 0.017% Cr, 0.015% in the first oxygen vanadium sulfate crystals
With 0.022% Na.
The first oxygen vanadium sulfate crystals of 100g are weighed, are added in 50ml ethanol solutions, agitator treating 3min, after filtering
The second oxygen vanadium sulfate crystals of gained are added to the pure vanadic sulfate saturated solution that 100ml concentration is 3.0mol/L, stirring is washed
3min is washed, filtering, 30min is dried at 60 DEG C, obtained 3rd sour vanadyl crystal, Cr in the 3rd sour vanadyl crystal<0.008%th,
Na<0.007%th, K<0.009%, water content is<25%, final vanadium recovery>85%；Compared to the first oxygen vanadium sulfate crystals,
The reduced rate that the reduced rate that the reduced rate of Cr is 52.9%, Na in 3rd oxygen vanadium sulfate crystals is 53.3%, K is 59.1%.
Example 2
Oxygen vanadium sulphate solution containing impurity element (Cr 0.072%, K 0.121%, Na 0.257%) was evaporated to
Saturation state, relative to 1mol vanadium ions in supersaturated solution, is taken 10L, adds 80g crystal seeds, carried out with 1.2 DEG C/h cooling rates
Decrease temperature crystalline, obtains the first oxygen vanadium sulfate crystals.Wherein, 0.006% Cr, 0.009% are contained in the first oxygen vanadium sulfate crystals
K and 0.006% Na.
The first oxygen vanadium sulfate crystals of 100g are weighed, are added in 80ml ethanol solutions, agitator treating 4min, after filtering
The second oxygen vanadium sulfate crystals of gained are added to the pure vanadic sulfate saturated solution that 80ml concentration is 3.5mol/L, agitator treating
4min, filtering, 46min is dried at 55 DEG C, obtained 3rd oxygen vanadium sulfate crystals, Cr in the 3rd oxygen vanadium sulfate crystals<
0.002%th, Na<0.003%th, K<0.004%, water content is<25%, final vanadium recovery>87%；Compared to the first sulfuric acid oxygen
Vanadium crystal, the reduced rate that the reduced rate that the reduced rate of Cr is 66.7%, Na in the 3rd oxygen vanadium sulfate crystals is 66.7%, K are
33.3%.
Example 3
Oxygen vanadium sulphate solution containing impurity element (Cr 0.457%, K 0.647%, Na 0.813%) was evaporated to
Saturation state, relative to 1mol vanadium ions in supersaturated solution, is taken 10L, adds 120g crystal seeds, carried out with 2 DEG C/h cooling rates
Decrease temperature crystalline, obtains the first oxygen vanadium sulfate crystals.Wherein, 0.033% Cr, 0.054% are contained in the first oxygen vanadium sulfate crystals
K and 0.042% Na.
The first oxygen vanadium sulfate crystals of 100g are weighed, are added in 100ml ethanol solutions, agitator treating 4.8min, mistake
The second oxygen vanadium sulfate crystals of gained are added to the pure vanadic sulfate saturated solution that 120ml concentration is 4.0mol/L after filter, are stirred
Washing 5min is mixed, filtering, 60min is dried at 50 DEG C, obtained 3rd oxygen vanadium sulfate crystals, Cr in the 3rd oxygen vanadium sulfate crystals<
0.016%th, Na<0.026%th, K<0.019%, water content is<20%, final vanadium recovery>92%；Compared to the first sulfuric acid oxygen
Vanadium crystal, the reduced rate that the reduced rate that the reduced rate of Cr is 51.5%, Na in the 3rd oxygen vanadium sulfate crystals is 51.9%, K are
54.8%.
In conclusion the method for impurity includes advantages below in the removal oxygen vanadium sulfate crystals of the present invention：
(1) invention directly removes impurity element from oxygen vanadium sulfate crystals, is eliminated compared with conventional method substantial amounts of preposition
The removal of impurities process of removal of impurities process in removal step, such as oxygen vanadium sulphate solution, even raw material stage, simplifies technique stream
Journey, reduces the production cost of oxygen vanadium sulfate crystals, has good economy.
(2) invention is also stripped of a part of crystallization water at the same time in the mistake of removal of impurities, indirectly reduces crystal water content, carries
The high content of vanadium of oxygen vanadium sulfate crystals, reduce further subsequent handling cost (drying, packaging, transport etc.).
(3) ethanol used in washing process can be with recycling, and the reagent price involved by whole technique is cheap, side
Method is simple, and impurity-eliminating effect is notable, is suitable for industrialized production.
Although by combining exemplary embodiment, the invention has been described above, those skilled in the art should be clear
Chu, in the case where not departing from the spirit and scope that claim is limited, can carry out the exemplary embodiment of the present invention each
Kind modifications and changes.
Claims (3)
- A kind of 1. method for removing impurity in oxygen vanadium sulfate crystals, it is characterised in that the described method comprises the following steps：Oxygen vanadium sulphate solution containing impurity element is evaporated to supersaturated solution, adds crystal seed, decrease temperature crystalline obtains the first sulphur Sour vanadyl crystal, in the oxygen vanadium sulphate solution containing impurity element containing 0.005%~0.1% Cr, 0.005%~ 0.1% Na and 0.005%~0.1% K；First oxygen vanadium sulfate crystals are washed with absolute ethyl alcohol, the second oxygen vanadium sulfate crystals, the absolute ethyl alcohol is obtained by filtration Liquid-solid ratio with first oxygen vanadium sulfate crystals is 0.5~1.0mL/g；Wash second oxygen vanadium sulfate crystals with pure vanadic sulfate saturated solution, the pure vanadic sulfate saturated solution with The liquid-solid ratio of second oxygen vanadium sulfate crystals is 1.0~1.5ml/g；Filter and dry, obtain the 3rd oxygen vanadium sulfate crystals, wherein, drying temperature is 50~60 DEG C, and the time is 30~60min.
- 2. the method according to claim 1 for removing impurity in oxygen vanadium sulfate crystals, it is characterised in that the pure sulfuric acid The concentration of vanadyl saturated solution is 3~4mol/L.
- 3. the method according to claim 1 for removing impurity in oxygen vanadium sulfate crystals, it is characterised in that Seed charge is 8~10g/L, 1~2 DEG C/h of cooling rate.
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|---|---|---|---|---|
| CN1202463A (en) * | 1997-06-17 | 1998-12-23 | 蔡晨波 | Process for high-yield synthesis of high content vanadylic sulfate |
| CN102198957A (en) * | 2010-03-26 | 2011-09-28 | 湖南维邦新能源有限公司 | Method for preparing vanadyl sulfate for vanadium ion redox flow battery |
| CN104310476A (en) * | 2014-09-30 | 2015-01-28 | 核工业北京化工冶金研究院 | Method for preparing vanadyl sulfate |
| CN105800688A (en) * | 2016-03-16 | 2016-07-27 | 河北钢铁股份有限公司承德分公司 | Method for preparing vanadyl sulfate through solid phase roasting |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202463A (en) * | 1997-06-17 | 1998-12-23 | 蔡晨波 | Process for high-yield synthesis of high content vanadylic sulfate |
| CN102198957A (en) * | 2010-03-26 | 2011-09-28 | 湖南维邦新能源有限公司 | Method for preparing vanadyl sulfate for vanadium ion redox flow battery |
| CN104310476A (en) * | 2014-09-30 | 2015-01-28 | 核工业北京化工冶金研究院 | Method for preparing vanadyl sulfate |
| CN105800688A (en) * | 2016-03-16 | 2016-07-27 | 河北钢铁股份有限公司承德分公司 | Method for preparing vanadyl sulfate through solid phase roasting |
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Application publication date: 20170215 Assignee: SICHUAN PAN YAN TECHNOLOGY Co.,Ltd. Assignor: Chengdu advanced metal material industry technology Research Institute Co.,Ltd. Contract record no.: X2024980003062 Denomination of invention: A method for removing impurities from vanadium oxysulfate crystals Granted publication date: 20180424 License type: Exclusive License Record date: 20240322 |